Under the influence of a twofold molar quantity of powdered sodium hydroxide in the presence of a few drops of methanol at room temperature dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides undergo a Stevens rearrangement with transfer of the reaction center, forming substituted amino alcohols with an allene group. Intramolecular cyclization of the products and concurrent hydration lead to the formation of a mixture of dialkyl(4-allyl-2,5-dihydrofuran-2-yl)amines and dialkylamino-3-allyl-4-hydroxybutanones with overall yields of 37-41%. During the aqueous-alkali cleavage of dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides the products from intramolecular cyclization were obtained with yields of 38-41%. Under the conditions both of Stevens rearrangement and of aqueous-alkali cleavage the secondary amines are also formed with yields of 15-17%. As nonamine products mixtures of compounds, which according to the IR spectra contain unconjugated and conjugated carbonyl groups, were obtained. The presence of an aldehyde group was established by a silver mirror reaction.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 354-360, March, 2009.
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Chukhadjian, E.O., Gabrielyan, A.S., Gevorkyan, A.R. et al. Behavior of dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides toward powdered sodium hydroxide and aqueous alkali. Chem Heterocycl Comp 45, 284–289 (2009). https://doi.org/10.1007/s10593-009-0276-9
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DOI: https://doi.org/10.1007/s10593-009-0276-9